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Polymeric networks are commonly used for various biomedical applications, from reconstructive surgery to wearable electronics. Some materials may be soft, firm, strong, or damping however, implementing all four properties into a single material to replicate the mechanical properties of tissue has been inaccessible. Herein, we present the A

We report on a new class of magnetoactive elastomers (MAEs) based on bottlebrush polymer networks filled with carbonyl iron microparticles. By synergistically combining solvent-free, yet supersoft polymer matrices, with magnetic microparticles, we enable the design of composites that not only mimic the mechanical behavior of various biological tissues but also permit contactless regulation of this behavior by external magnetic fields. While the bottlebrush architecture allows to finely tune the matrix elastic modulus and strain-stiffening, the magnetically aligned microparticles generate a 3-order increase in shear modulus accompanied by a switch from a viscoelastic to elastic regime as evidenced by a ca. 10-fold drop of the damping factor. The developed method for MAE preparation through solvent-free coinjection of bottlebrush melts and magnetic particles provides additional advantages such as injection molding of various shapes and uniform particle distribution within MAE composites. The synergistic combination of bottlebrush network architecture and magnetically responsive microparticles empowers new opportunities in the design of actuators and active vibration insulation systems.

In this work using dissipative particle dynamics simulations with explicit treatment of polar species we demonstrate that the molecular nature of dielectric media has a significant impact on swelling and collapse of a polyelectrolyte chain in a dilute solution. We show that the small-scale effects related to the presence of polar species lead to the intensification of the electrostatic interactions when the charges are close to each other and/or their density is high enough. As a result, the electrostatic strength , usually regarded as the main parameter governing the polyelectrolyte chain collapse, does not have a universal meaning: the value of λ at which the coil-to-globule transition occurs is found to be dependent on the specific fixed value of the solvent bulk permittivity e while varying the monomer unit charge Q and vice versa. This effect is observed even when the backbone and the counterions have the same polarity as the solvent beads, i.e. no dielectric mismatch is present. The reason for such behavior is rationalized in terms of the “effective” dielectric permittivity eeff which depends on the volume fraction φ of charged units inside the polymer chain volume; using eeff instead of e collapses all data onto one master curve describing the chain shrinking with λ. Furthermore, it is shown that a polar chain adopts less swollen conformations in the polyelectrolyte regime and collapses more easily compared to a non-polar chain.

The nanostructures of polyelectrolyte complexes (PECs) fabricated from a series of rationally designed oppositely charged amphiphilic random copolymers with variable comonomer compositions were stu...

The structure and properties of polysiloxane dendrimer melts are studied by extensive atomistic molecular dynamics simulations. Two homologous series differing in the spacer length are considered. In the first series the dendrimer spacers are the shortest ones, comprising only one oxygen atom, while in the second series the spacers consist of two oxygen atoms with the silicon atom in between. Melts of the dendrimers from the 3rd up to the 6th generation number are modelled in a wide temperature range from 273 to 600 K. A comparative study of the macroscopic melt characteristics such as the melt density and thermal expansion coefficients is performed for the two series. Analysis of the dendrimer structure in melts and in the isolated state shows that intermolecular interactions and interpenetration of dendrimer molecules in melts hardly affect the dendrimer interior organization. However, the presence of neighboring molecules significantly slows down their intramolecular dynamics in melts in comparison with that of isolated dendrimers. An increasing generation number causes an increase of the radius of the dendrimer interior region unavailable for neighboring molecules, which starts to exceed the length of the peripheral interpenetration layer for high-generation dendrimers; this fact could lead to different mechanisms of melt dynamics for lower and higher generation dendrimers.

Here we report on a light triggered remote control of microgel size in the presence of photosensitive surfactant. The hydrophobic tail of the cationic surfactant contains azobenzene group that undergoes a reversible photo-isomerization reaction from a trans-to a cis-state accompanied by a change in the hydrophobicity of the surfactant. We have investigated light assisted behaviour and the complex formation of the microgels with azobenzene containing surfactant over the broad concentrational range starting far below and exceeding several times of the critical micelle concentration (CMC). At small surfactant concentration in solution (far below CMC), the surfactant in the trans-state accommodates within the microgel causing its compaction, while the cis-isomer desorbs out of microgel resulting in its swelling. The process of the microgel size change can be described as swelling on UV irradiation (trans-cis isomerization) and shrinking on irradiation with blue light (cis-trans isomerization). However, at the surfactant concentrations larger than CMC, the opposite behaviour is observed: the microgel swells on blue irradiation and shrinks during exposure to UV light. We explain this behaviour theoretically taking into account isomer dependent micellization of surfactant within the microgels. Published by AIP Publishing.

A series of copolymers with controlled monomer sequences are prepared via the reversible addition–fragmentation chain transfer polymerization of tert-butyl carbamate (Boc)-l-alanine (VBA) and Boc-l...

A possibility of microphase separation in a blend of oppositely charged polyelectrolytes, being immiscible when uncharged, is studied theoretically and by means of dissipative particle dynamics (DP...

A review of the latest theoretical advances in the description of magnetomechanical effects and phenomena observed in magnetoactive elastomers (MAEs), i.e., polymer networks filled with magnetic micro- and/or nanoparticles, under the action of external magnetic fields is presented. Theoretical modeling of magnetomechanical coupling is considered on various spatial scales: from the behavior of individual magnetic particles constrained in an elastic medium to the mechanical properties of an MAE sample as a whole. It is demonstrated how theoretical models enable qualitative and quantitative interpretation of experimental results. The limitations and challenges of current approaches are discussed and some information about the most promising lines of research in this area is provided. The review is aimed at specialists involved in the study of not only the magnetomechanical properties of MAEs, but also a wide range of other physical phenomena occurring in magnetic polymer composites in external magnetic fields.

Dielectric properties of two series of magnetoactive elastomers (MAEs) based on a soft silicone matrix containing 35 vol% of magnetic particles were studied experimentally in a wide temperature range. In the first series, a hybrid filler representing a mixture of magnetically hard NdFeB particles of irregular shape and an average size of 50 μm and magnetically soft carbonyl iron (CI) of 4.5 μm in diameter was used for MAE fabrication. MAEs of the second series contained only NdFeB particles. The presence of magnetically hard NdFeB filler made it possible to passively control MAE dielectric response by magnetizing the samples. It was shown that although the hopping mechanism of MAEs conductivity did not change upon magnetization, a significant component of DC conductivity appeared in the magnetized MAEs presumably due to denser clustering of interacting particles resulting in decreasing interparticle distances. The transition from a non-conducting to a conducting state was more pronounced for hybrid MAEs containing both NdFeB and Fe particles with a tenfold size mismatch. Hybrid MAEs also demonstrated a considerable increase in the real part of the complex relative permittivity upon magnetization and its asymmetric behavior in external magnetic fields of various directions. The effects of magnetic filler composition and magnetization field on the dielectric properties of MAEs are important for practical applications of MAEs as elements with a tunable dielectric response.

Polymers 13(4), 606 (1-15) (2021). doi:10.3390/polym13040606, A series of carbosilane dendrimers of the 4th, 6th, and 7th generations with a terminal trimethylsilylsiloxane layer was synthesized. Theoretical models of these dendrimers were developed, and equilibrium dendrimer conformations obtained via molecular dynamics simulations were in a good agreement with experimental small-angle X-ray scattering (SAXS) data demonstrating molecule monodispersity and an almost spherical shape. It was confirmed that the glass transition temperature is independent of the dendrimer generation, but is greatly affected by the chemical nature of the dendrimer terminal groups. A sharp increase in the zero-shear viscosity of dendrimer melts was found between the 5th and the 7th dendrimer generations, which was qualitatively identical to that previously reported for polycarbosilane dendrimers with butyl terminal groups. The viscoelastic properties of high-generation dendrimers seem to follow some general trends with an increase in the generation number, which are determined by the regular branching structure of dendrimers., Published by MDPI, Basel

We studied the conformational behavior of silicon-containing dendrimers during their adsorption onto a flat impenetrable surface by molecular dynamics (MD) simulations. Four homologous series of dendrimers from the 4th up to the 7th generations were modeled, namely, two types of carbosilane dendrimers differing by the functionality of the core Si atom and two types of siloxane dendrimers with different lengths of the spacers. Comparative analysis of the fractions of adsorbed atoms belonging to various structural layers within dendrimers as well as density profiles allowed us to elucidate not only some general trends but also the effects determined by dendrimer specificity. In particular, it was found that in contrast to the carbosilane dendrimers interacting with the adsorbing surface mainly by their peripheral layers, the siloxane dendrimers with the longer –O–Si(CH3)2–O spacers expose atoms from their interior to the surface spreading out on it. These findings are important for the design of functional materials on the basis of silicon-containing dendrimers.

Elongations of magnetoactive elastomers (MAEs) under ascending&ndash, descending uniform magnetic fields were studied experimentally using a laboratory apparatus specifically designed to measure large extensional strains (up to 20%) in compliant MAEs. In the literature, such a phenomenon is usually denoted as giant magnetostriction. The synthesized cylindrical MAE samples were based on polydimethylsiloxane matrices filled with micrometer-sized particles of carbonyl iron. The impact of both the macroscopic shape factor of the samples and their magneto-mechanical characteristics were evaluated. For this purpose, the aspect ratio of the MAE cylindrical samples, the concentration of magnetic particles in MAEs and the effective shear modulus were systematically varied. It was shown that the magnetically induced elongation of MAE cylinders in the maximum magnetic field of about 400 kA/m, applied along the cylinder axis, grew with the increasing aspect ratio. The effect of the sample composition is discussed in terms of magnetic filler rearrangements in magnetic fields and the observed experimental tendencies are rationalized by simple theoretical estimates. The obtained results can be used for the design of new smart materials with magnetic-field-controlled deformation properties, e.g., for soft robotics.

International audience; The instability of a homogeneous complex coacervate phase induced by incompatibility of oppositely charged polyelectrolytes is studied by means of the random phase approximation (RPA) and the scaling approach. It is found that in a poor solvent for both polyions their short-range mutual repulsions may result in the formation of a microphase separated structure at low salt concentrations cs. At high cs, a decomposition of the homogeneous coacervate into two macroscopic globular phases enriched either with polyanions or with polycations takes place. Both the RPA and scaling estimations predict the period of the microphase separated structure on the order of a few nanometers in the vicinity of the spinodal. The binodal of macroscopic phase separation of the coacervate and the spinodal with respect to the microphase separation are calculated, and the phase diagram of the coacervate is constructed in terms of salt concentration and incompatibility of polyions. The possibility of experimental observation of a microsegregated coacervate is discussed.

A series of magnetoactive elastomer (MAE) coatings consisting of a silicone matrix and carbonyl iron particles (3–5 μm in diameter) have been synthesized and their hydrophobic properties have been investigated in various magnetic fields of disk-shaped permanent NdFeB magnets. Concentration of magnetic filler in MAEs has been varied in the range of 63–76 mass%. Both isotropic samples and structured samples synthesized in the magnetic field of 80 mT have been obtained. It has been shown that application of a magnetic field induces structuring of the filler on the surface of MAE coatings, resulting in formation of mountain-like microstructures. Microstructure relief on coating surfaces leads to an increase of a water contact angle which could be varied from 110° ± 10° at zero field up to 163° ± 2° at 600 mT. The contact angle at the maximum field increases with iron filler content and with softening of the polymer matrix.

Rheological melt behavior of carbosilane dendrimers from the 3rd up to the 8th generation has been studied experimentally under steady shear, creep and dynamic oscillatory shear. Six orders of magnitude jump in viscosity was found between the 5th and the 6th generations. While the low-generation dendrimer melts demonstrate Newtonian behavior in a wide temperature range of 20÷80 °C, starting from the 6 t h generation, the dendrimer melts lose their ability to freely flow and acquire properties of a material with a well-pronounced yield stress. The storage modulus of high-generation dendrimer melts by far exceeds the loss modulus, furthermore, its value increases with temperature. It is demonstrated that the high-generation carbosilane dendrimers in bulk can be considered a polymer material with unique properties and as that, could find new applications in high-tech areas, in particular, as matrices for sensors.

Magnetodielectric properties of magnetoactive elastomers comprising micrometer-sized iron particles dispersed in compliant elastomer matrices are experimentally studied in stepwise time-varying dc magnetic fields. It is found that imposition of magnetic field significantly increases both the effective lossless permittivity of these composite materials as well as their effective conductivity. These magnetodielectric effects are more pronounced for larger concentrations of soft-magnetic filler particles and softer elastomer matrices. The largest observed relative change of the effective dielectric constant in the maximum magnetic field of 0.57 T is of the order of 1000%. The largest observed absolute change of the loss tangent is approximately 0.8. The transient response of the magnetodielectric effect to a step magnetic-field excitation can be rather complex. It changes from a simple monotonic growth with time for small magnetic-field steps ( 0.3 T). The settling time to the magnetic-field step excitation can reach roughly 1000 s and it depends on the applied magnetic field and sample composition. There is also significant hysteresis of the magnetodielectric effect on the externally applied magnetic field. These findings are attributed to the rearrangement of ferromagnetic filler particles in external magnetic fields. The results will be useful for understanding and predicting the transient behavior of magnetoactive elastomers in applications where the control magnetic field is time dependent.

The phenomenon of spinodal decomposition in weakly charged polyelectrolyte solutions is studied theoretically within the random phase approximation. A novel feature of the theoretical approach is that it accounts for the effects of ionic association, i.e. ion pair and multiplet formation between counterions and ions in polymer chains, as well as the dependence of local dielectric permittivity on the polymer volume fraction Φ. The main focus is on the spinodal instability of polyelectrolyte solutions towards microscopic phase separation. It has been shown that increasing the binding energy of ions decreases the classical microphase separation region (possible at low polymer concentrations) due to the effective neutralization of the chains. A qualitatively new type of microphase separation is found in the presence of a dielectric mismatch between polymer and solvent. This new branch of microphase separation is realized at high polymer concentrations where ion association processes are the most pronounced. Typical microstructures are shown to have a period of a few nanometers like in ionomers. The driving force for the microphase formation of a new type is more favourable ion association in polymer-rich domains where ionomer-type behavior takes place. Effective attraction due to ion association promotes microscopic as well as macroscopic phase separation, even under good solvent conditions for uncharged monomer units of polymer chains. Polyelectrolyte-type behavior at low Φ and ionomer-type behavior at high Φ result in the presence of two critical points on the phase diagrams of polyelectrolyte solutions as well as two separate regions of possible microscopic structuring. Our predictions on the new type of microphase separation are supported by experimental data on polymer solutions, membranes and gels.

We report on light sensitive microgel particles that can change their volume reversibly in response to illumination with light of different wavelengths. To make the anionic microgels photosensitive we add surfactants with a positively charged polyamine head group and an azobenzene containing tail. Upon illumination, azobenzene undergoes a reversible photo-isomerization reaction from a trans- to a cis-state accompanied by a change in the hydrophobicity of the surfactant. Depending on the isomerization state, the surfactant molecules are either accommodated within the microgel (trans- state) resulting in its shrinkage or desorbed back into water (cis-isomer) letting the microgel swell. We have studied three surfactants differing in the number of amino groups, so that the number of charges of the surfactant head varies between 1 and 3. We have found experimentally and theoretically that the surfactant concentration needed for microgel compaction increases with decreasing number of charges of the head group. Utilization of polyamine azobenzene containing surfactants for the light triggered remote control of the microgel size opens up a possibility for applications of light responsive microgels as drug carriers in biology and medicine.

The conformational behavior of an isolated semiflexible dipolar chain has been studied by molecular dynamics simulations. The dipolar chain was modeled as a backbone chain of charged beads, each containing an oppositely charged unit connected to it by a rigid spring. The main focus was on the effect of the backbone chain rigidity and the size of the charged groups on the morphology of the collapsed states of the chain formed in low-polar media where the electrostatic interactions are essential. It has been found that the stable globular conformations of the long chain of N = 256 backbone beads are a toroid and an elliptical globule. The macroscopic parameters (such as the radius of gyration and shape factors) as well as the local characteristics of these conformations (radial density distributions of ions, orientational correlations of chain segments, dipoles etc.) are studied depending on the chain stiffness. The regions of stability of a torus and an elliptical globule are found for the dipolar chains with variable dipole length and stiffness, which depend on the strength of electrostatic interactions. It has been shown that a size asymmetry of oppositely charged beads destabilizes globular states favoring elongated chain conformations. A coexistence of various metastable states was demonstrated for shorter chains of N = 128, 64, and 32.

The magnetodielectric response of magnetoactive elastomers (MAEs) in its dependence on filler concentration, magnetic field, and test frequency is studied experimentally. MAEs are synthesized on the basis of a silicone matrix filled with spherical carbonyl iron particles characterized by a mean diameter of 4.5 &micro, m. The concentration of the magnetic filler within composite materials is equal to 70, 75, and 80 mass%. The effective lossless permittivity &epsilon, &prime, as well as the dielectric loss tan&delta, grow significantly when the magnetic field increases. The permittivity increases and the dielectric loss decreases with increasing filler concentration. In the measurement frequency range between 1 kHz and 200 kHz, the frequency hardly affects the values of &epsilon, and tan&delta, in the absence of a magnetic field. However, both parameters decrease considerably with the growing frequency in a constant magnetic field. The more strongly the magnetic field is applied, the larger the change in permittivity and loss tangent at the same test frequency is observed. An equivalent circuit formulation qualitatively describes the main tendencies of the magnetodielectric response.

In this Note, we study the total conservative force {instead of pure electrostatic force as it was carried out in the work by Gavrilov [J. Chem. Phys. 152, 164101 (2020)]} acting on two charges in a polar liquid using dissipative particle dynamics and coarse-grained molecular dynamics simulations. We show that such force (instead of the electrostatic force) obeys Coulomb's law at large distances between the charges. Apparently, the dielectric response of a polar liquid (at least, within such coarse-grained models) can be decomposed into two contributions: the reorientation of the dipoles (i.e., electrostatic contribution) and the density redistribution (i.e., volume interaction contribution).

A joint theoretical and experimental study is devoted to the swelling and electrical conductivity of highly charged polyelectrolyte (PE) gels in media of different polarity. Deprotected poly(tert-butyl carbamate l-alanine) gels provided with fluorine, bromine, chlorine, sulfate, and trifluoroacetic counteranions demonstrated different conductivity in aqueous medium as well as solvent uptake in water/methanol mixtures. Counterion specificity in PE gel properties was theoretically explained in the framework of the model which treats ion association within the network as a two-stage process. Manning-type condensation, being the first condensation stage not affected by counterion type, provides understanding of a gel maximal swelling at intermediate degrees of gel ionization f and a slight gel contraction at f tending to unity, which were earlier observed in experimental investigations. The second ion association stage is an ion pairing influenced by the kind of counterion. Since a considerable fraction of io...

The structure of a thin magnetoactive elastomeric (MAE) film adsorbed on a solid substrate is studied by molecular dynamics simulations., The structure of a thin magnetoactive elastomeric (MAE) film adsorbed on a solid substrate is studied by molecular dynamics simulations. Within the adopted coarse-grained approach, a MAE film consists of magnetic particles modeled as soft-core spheres, carrying point dipoles, connected by elastic springs representing a polymer matrix. MAE films containing 20, 25 and 30 vol% of randomly distributed magnetic particles are simulated. Once a magnetic field is applied, the competition between dipolar, elastic and Zeeman forces leads to the restructuring of the layer. The distribution of the magnetic particles as well as elastic strains within the MAE films are calculated for various magnetic fields applied perpendicular to the film surface. It is shown that the surface roughness increases strongly with growing magnetic field. For a given magnetic field, the roughness is larger for the softer polymeric matrix and exhibits a nonmonotonic dependence on the magnetic particle concentration. The obtained results provide a better understanding of the MAE surface structuring as well as possible guidelines for fabrication of MAE films with a tunable surface topology.

A comparative analysis of intramolecular dynamics of four types of isolated dendrimers from the fourth to the seventh generations belonging to the siloxane and carbosilane families, differing in spacer length, core functionality, and the type of chemical bonds, has been performed via atomic molecular dynamics simulations. The average radial and angular positions of all Si branching atoms of various topological layers within the dendrimer interior, as well as their variations, have been calculated, and the distributions of the relaxation times of their radial and angular motions have been found. It has been shown that the dendrons of all the dendrimers elongate from the center and decrease in a solid angle with an increasing generation number. The characteristic relaxation times of both angular and radial motions of Si atoms are of the order of a few nanoseconds, and they increase with an increasing generation number and decrease with temperature, with the angular relaxation times being larger than the radial ones. The relaxation times in the carbosilanes are larger than those in the siloxanes. The rotational angle dynamics of the carbosilane dendrimers show that the chain bending is mainly realized via trans-gauche transitions in the Si branching bonds.

Conformational behavior of a single strongly charged polyelectrolyte chain in a dilute solution is studied by molecular dynamics simulations. The novel feature of the model is variation of the excluded volume of counterions for investigating its effect on the chain conformation, especially in low-polar media. It has been confirmed that the chain with conventional counterions collapses into a dense globule with increasing electrostatic interactions. However, if the counterions are bulky enough, they prevent the chain collapse even in media with strong electrostatic interactions. They stay bound in the vicinity of the backbone of the chain that adopts a swollen conformation. In this conformation, the scaling relation for the polymer dimensions with the chain length is the same as for neutral macromolecules in a good solvent, however the polyelectrolyte chain complexed with bulky counterions has a larger gyration radius than its uncharged analogue due to the excluded volume of the counterions contributing to the chain rigidity. Study of the counterion mobility has shown that, similar to the conventional counterions, the bulky counterions do not form stable ion pairs with ions on the polymer chain even in media with strong electrostatic interactions, but rather freely move along the chain backbone. In solutions containing mixtures of counterions with a bimodal size distribution, the conformations of linear polyelectrolytes depend considerably on the fraction of bulky counterions. Furthermore, a kind of intramolecular microphase separation can take place within a polyelectrolyte globule with the formation of a core-shell particle: the smaller counterions concentrate within the globular core while the bulkier counterions form a shell on the globule surface. The stability of the core-shell globule depends on the relative size of the counterions as well as their fractions in the solution. Thus, fine tuning of the balance between the counterion excluded volume and the electrostatic interactions opens new ways for controlling the conformational behavior of polyelectrolytes.

This chapter introduces composite smart materials known as magnetoactive (MAEs) or magnetorheological elastomers. It starts by defining these materials and distinguishing them from relevant magnetorheological fluids and ferrofluids. It then gives the overview of constitutive materials for the polymer matrix and filler particles. Next, the influence of external magnetic field on physical properties of MAEs is discussed. The emphasis is made on mechanical properties, which are the most important for real-world applications. In particular, magnetomechanical effects such as magnetostriction, magnetodeformation, and magnetorheological effect are discussed. The magnetic Payne effect is presented as an example of a nonlinear behavior. Electromagnetic and acoustic properties are also considered. The chapter finishes with the brief discussion of the future prospects in research and development of MAEs.

Hysteresis in dynamic modulus, loss factor and normal forces of magnetoactive elastomers (MAEs) comprising various proportions of small (3–5 μm) and large (50–60 μm) ferromagnetic particles are experimentally studied using dynamic torsion performed at a fixed oscillation frequency in varying DC magnetic fields. It is shown that hysteresis is a characteristic feature of MAEs observed both under increasing/decreasing magnetic field strength and increasing/decreasing strain amplitude. This hysteresis is attributed to the specific rearrangement of the magnetic filler network under simultaneously applied magnetic field and shear deformation. Rheological properties of the magnetic filler network formed in the magnetic field and, therefore, the rheological properties of MAEs depend strongly on the filler composition and the magnetic field magnitude. Larger magnetic particles and higher magnetic fields provide stronger magnetic networks. Both factors result in the extension of the linear viscoelastic regime to larger strain amplitudes and lead to higher values of shear storage and loss moduli. It is found that the hysteresis width maximises at an intermediate magnetic field where it is attributed to the balance between elastic and magnetic particle interactions. This is apparently where the most significant restructuring of the magnetic network occurs. The hysteresis width decreases with increasing fraction of large particles in the magnetic filler. The loss factor grows significantly when the magnetic network is physically broken by large strains γ > 1%. A huge (more than one order of magnitude) increase of normal force at maximum magnetic field strengths is observed. It is predicted that any physical quantity depending on the internal structuring of the magnetic filler should demonstrate hysteresis either with a changing magnetic field and constant deformation amplitude or under variable deformation in a constant magnetic field.

The dynamic shear modulus of magnetoactive elastomers containing 70 and 80 mass % of carbonyl iron microparticles is measured as a function of strain amplitude via dynamic torsion oscillations in various magnetic fields. The results are presented in terms of the mechanical energy density and considered in the framework of the conventional Kraus model. The form exponent of the Kraus model is further related to a physical model of Huber et al. [Huber et al., J. Phys.: Condens. Matter 8, 409 (1996)] that uses a realistic representation for the cluster network possessing fractal structure. Two mechanical loading regimes are identified. At small strain amplitudes the exponent \ensuremath{\beta} of the Kraus model changes in an externally applied magnetic field due to rearrangement of ferromagnetic-filler particles, while at large strain amplitudes, the exponent \ensuremath{\beta} seems to be independent of the magnetic field. The critical mechanical energy characterizing the transition between these two regimes grows with the increasing magnetic field. Similarities between agglomeration and deagglomeration of magnetic filler under simultaneously applied magnetic field and mechanical shear and the concept of jamming transition are discussed. It is proposed that the magnetic field should be considered as an additional parameter to the jamming phase diagram of rubbers filled with magnetic particles.

The dynamic modulus and the loss factor of magnetorheological elastomers (MREs) of various compositions and anisotropies are studied by dynamic torsion oscillations performed in the absence and in the presence of an external magnetic field. The emphasis is on the Payne effect, i.e. the dependence of the elastomer magnetorheological characteristics on the strain amplitude and their evolution with cyclically increasing and decreasing strain amplitudes. MREs are based on two silicone matrices differing in storage modulus (soft, G' ∼ 10(3) Pa, and hard, G' ∼ 10(4) Pa, matrices). For each matrix, the concentration of carbonyl iron particles with diameters of 3-5 μm was equal to 70 and 82 mass% (22 and 35 vol%, respectively) in the composite material. Samples for each filler content, isotropic and aligned-particles, are investigated. It is found that the Payne effect significantly increases in the presence of an external magnetic field and varies with the cyclical loading which reaches saturation after several cycles. The results are interpreted as the processes of formation-destruction-reformation of the internal filler structure under the simultaneously applied mechanical force and magnetic field. Impacts of matrix elasticity and magnetic interactions on the filler alignment are elucidated.

Magneto-active elastomers (MAEs) based on a silicon polymer matrix filled with magnetic carbonyl iron microparticles have been synthesized. Both isotropic samples and samples micro-structured by an external magnetic field have been obtained. The radio-absorbing properties of the MAEs have experimentally been studied in the frequency range 2–10 GHz and at the central work frequency 30 GHz of the range 26–38 GHz in the absence and in the presence of an external magnetic field of 0.3 T. It has been shown that both the reflection and transmission coefficients of the MAEs change considerably when the magnetic field is applied, besides, their values strongly depend on the direction of the magnetic field as well as on the internal filler structure of MAEs. The developed MAEs could be used as controllable by an external magnetic field radio-shielding or polarizing covers.

We report a combined experimental and theoretical study on the swelling behavior of polyelectrolyte gels with various types of counterions. Experimental research was focused on poly(methacrylic acid) and poly(acrylic acid) gels in methanol neutralized with different bases providing sodium, cesium, tetramethyl-, tetraethyl- or tetrabutylammonium counterions. The novelty of the theoretical treatment is that the counterion size is explicitly taken into account as well as the dependence of the ion association constant on the volume fraction of polymer within the gel. We demonstrate that, depending on the counterion size, three different regimes of the gel behavior are realized. In case of bulky tetrabutylammonium counterions the gel swells upon ionization. For small counterions (Na+, Cs+) the gel swelling at low ionization degrees is succeeded by its collapse. New type of behavior was observed and theoretically described for the gels with counterions of intermediate sizes (tetramethyl- and tetraethylammonium)...

Conformational behaviour of hydrophobically modified (HM) polymer gels in solutions of nonionic surfactants is studied theoretically. A HM gel contains hydrophobic side chains (stickers) grafted to its subchains. Hydrophobic stickers are capable to aggregate into joint micelles with surfactant molecules. Micelles containing more than one sticker serve as additional physical cross-links of the network, and their formation causes gel shrinking. In the proposed theoretical model, the interior of the gel/surfactant complex is treated as an array of densely packed spherical polymer brushes consisting of gel subchains tethered to the surface of the spherical sticker/surfactant micelles. Effect of stickers length and grafting density, surfactant concentration and hydrophobicity on gel swelling as well as on hydrophobic association inside it is analyzed. It is shown that increasing surfactant concentration can result in a gel collapse, which is caused by surfactant-induced hydrophobic aggregation of stickers, and a successive gel reswelling. The latter should be attributed to a growing fraction of surfactants in joint aggregates and, hence, increasing number of micelles containing only one sticker and not participating in gel physical cross-linking. In polyelectrolyte (PE) gels hydrophobic aggregation is opposed by osmotic pressure of mobile counterions, so that at some critical ionization degree hydrophobic association is completely suppressed. Hydrophobic modification of polymers is shown to open new ways for controlling gel responsiveness. In particular, it is discussed that incorporation of photosensitive groups into gel subchains and/or surfactant tail could give a possibility to vary the gel volume by light. Since hydrophobic aggregation regularities in gels and solutions are common, we hope our findings will be useful for design of polymer based self-healing materials as well.

The conformational behavior of a single AB block copolymer is studied by Monte Carlo simulation. The A-A and A-B interactions have the character of excluded volume interactions while the B units attract each other; the attractive B blocks can move along the chain. The collapse transition of the chain with increasing attraction between the B units is analyzed. Intrachain separation of the A and B units takes place in the course of the chain collapse with the formation of "globule with a tail" conformations. The globule is formed by the attractive moving B blocks while the tail consists of the swollen A segments. The model of AB block copolymer with moving B blocks can describe the behavior of interpolymer complexes between a long macromolecule and shorter polymer chains.

We develop a theory of microphase separation in a solution precipitate of flexible AB block copolymers consisting of charged (A) and neutral (B) blocks which are complexed with oppositely charged linear chains (C) via electrostatic interactions. We analyze regimes of selective solvents: the solvent is Θ for the A blocks and the C chains, whereas it is poor for the B blocks. Despite the selectivity, stoichiometric complexes precipitate because of fluctuations induced electrostatic attraction. Depending on composition of the diblock copolymer, selectivity of the solvent and fraction of charged groups, direct and inverse spherical, cylindrical and lamellar structures can be stable in the precipitant. Phase diagrams are constructed in the strong segregation approximation. Morphological transitions induced by changes of solvent quality and fraction of charged groups are predicted.

New composite materials consisting of polymer matrix with PZT and NdFeB microparticles were prepared and investigated in the work. It was found that magnetic properties such as saturation magnetization, coercivity, permeability, depend on mass concentration of the ferromagnetic particles in the samples. Also it was found that all samples had electrical polarization in DC external electric field. The electric properties such as coercivity, remanent polarization, the maximum polarization value, had changes in the external constant magnetic field 1.1 kOe. These changes depended on both concentrations of ferromagnetic and ferroelectric particles. This type of magnetoelectric transformation allows us to classify new materials as multiferroic materials. These new composite materials can easily be prepared of any shape, the final materials are flexible and resistant to external chemical influences. The area of application of new multiferroic materials varies from sensors to autonomous energy sources.

We report a combined experimental and theoretical study of micellization of block copolymer with hydrophilic nonionic corona-forming blocks and weak polyelectrolyte (wPE) core-forming blocks with pH-triggered solubility in aqueous solutions. We demonstrate that in addition to micelles with neutral cores, there exist two other types of micelles with PE- or ionomer-like cores, in which monovalent counterions are released or condensed on core wPE block, respectively. The transition between the two types of micelles occurred upon changes in ionization of the PE core block and resulted in nonmonotonous changes of aggregation number as a function of pH. Such micelles with stimulus responsive cores represent promising nanocarriers for controlled delivery applications.

The combination of polymers with magnetic particles displays novel and often enhanced properties compared to the traditional materials. They can open up possibilities for new technological applications. The magnetic field sensitive elastomers represent a new type of composites consisting of small particles, usually from nanometer range to micron range, dispersed in a highly elastic polymeric matrix. In this paper, we show that in the presence of built-in magnetic particles it is possible to tune the elastic modulus by an external magnetic field. We propose a phenomenological equation to describe the effect of the external magnetic field on the elastic modulus. We demonstrate the engineering potential of new materials on the examples of two devices. The first one is a new type of seals fundamentally different from those used before. In the simplest case, the sealing assembly includes a magnetoelastic strip and a permanent magnet. They attract due to the magnetic forces. This ensures that due to high elasticity of the proposed composites and good adhesion properties, the strip of magnetoelastic will adopt the shape of the surface to be sealed, this fact leading to an excellent sealing. Another straightforward application of the magnetic composites is based on their magnetic field dependent elastic modulus. Namely, we demonstrate in this paper the possible application of these materials as adjustable vibration dampers. Copyright © 2007 John Wiley & Sons, Ltd.

The new generation of magnetic elastomers represents a new type of composites, consisting of small (mainly nano and micron-sized) magnetic particles dispersed in a highly elastic polymeric matrix. The combination of polymers with magnetic materials displays novel and often enhanced properties. Highly elastic magnetic composites are quite new and understanding of the behavior of these materials depending on the composition, external conditions, and the synthesis processes is still missing. Thus, the aim of this work is the study of fundamental principles governing the preparation of these materials as well as their structure and elastic properties. Copyright © 2007 John Wiley & Sons, Ltd.

Magnetorheological elastomers (MRE) have been synthesized on the basis of a silicon compound and a mixture of carbonyl iron particles of sizes 3–5 and 40–80 μm. Their viscoelastic properties have been studied by dynamic shear oscillations of various amplitudes on a stress controlled rheometer. The magnetic response of the obtained materials has been examined in a magnetic field applied perpendicular to the shear plane. It has been shown that under applied magnetic field both the storage G′ and loss G″ moduli became strain-dependent. The values of G′ and G″ decrease with strain, while their ratio (the loss factor), G″/G′, growths with strain. The higher magnetic field is the more pronounced the strain dependence is. At small strain (up to 1%) MRE demonstrate a giant (more than 10 times) increase of the moduli. Some features of hysteretic behavior of MRE under simultaneously applied magnetic field and external mechanical force have been elucidated. Temperature has a negligible effect on viscoelastic properties and stability of the developed MRE. A damper on the basis of MRE has been designed and its properties have been examined.

We report on the theoretical study of interaction of ionic surfactants with oppositely charged microgel particles in dilute solutions. Two approaches are proposed. Within the first approach, the micellization of the surfactants inside the microgel is taken into account while the second model focuses on the hydrophobic interactions of the surfactant tails with the hydrophobic parts of microgel subchains. It has been shown that microgels effectively absorb surfactant ions. At low surfactant concentration this absorption is realized due to an ion exchange between microgel counterions and surfactant ions. The ion exchange is significantly affected by the amount of the microgel counterions initially trapped within the microgel particles which depends on the size of the microgel, its ionization degree, cross-linking density as well as polymer concentration in the solution. Increase of the surfactant concentration causes contraction of the microgels, which can be realized as either a continuous shrinking or a jump-like collapse transition depending on the system parameters. In the collapsed state additional absorption of surfactants by microgels takes place due to an energy gain from micellization or hydrophobic interactions. This leads to microgel precipitation and successive microgel overcharging at an excess of the surfactant in the solution. The theoretical results are compared with the existing experimental data, in particular, on photosensitive surfactant/microgel complexes.

In this paper we study the influence of the formation of intrachain ion pairs (salt bonds) and the distribution of counterions on the behavior of single polyampholyte chains in a dilute solution. It has been shown that neutral polyampholyte chains can undergo jump-like collapse transition from the swollen state to the globular state with the formation of ion pairs between oppositely charged ions of the chain. A polyampholyte chain with an excess charge shows the behavior of a conventional polyelectrolyte chain and counterions play an important role in the chain behavior. We distinguish three possible states of counterions: free counterions inside and outside the macromolecule, and a bound state of counterions forming ion pairs with the corresponding ions of the polymer chain. We found a non-monotonous behavior of the chain upon increasing the excess charge on the chain: the chain swells from a compact state to elongated conformation and shrinks again to the compact state when the excess charge of the chain is increased.

Full Paper: In this paper we consider the influence of counterion distribution on the behavior of polyelectrolyte systems. We propose the unified model to describe and to compare the swelling and collapse properties of single polyelectrolyte chains in dilute solutions, microgel particles of various molecular masses, and (as a limiting case) macroscopic gels. A novel feature of the new approach is that we distinguish three possible states of counterions: free countertions inside and outside the poly ther macromolecule and a bound state of counterions forming ion pairs with corresponding ions of polymer chains. The latter possibility becomes progressively important when macromolecules or gels shrink. In this case the formation of a supercollapsed state is possible, when all couterions are trapped and form ion pairs. On the other hand, the fact that counterions can float in the outer solution affects essentially the conformation of polyelectrolyte chains in dilute solutions of good where practically all counter ions can escape the space inside polymer coils and the repulsion between uncompensated charges plays an important role in the chain behavior.

We have investigated the swelling behavior of polyelectrolyte gels in a low-molecular-weight solvent taking into account the possibility of intragel phase separation. We have shown that, as for the case of a neutral gel considered recently by Moerkerke et al., the coexistence of two phases differing by polymer concentration can also take place inside the polyelectrolyte gel if the amount of solvent is not enough to ensure its free swelling. The phase diagrams for polyelectrolyte gels with various degrees of ionization and with various degrees of stiffness of the gel subchains have been calculated. It has been shown that the region of stability of the two-phase gel increases significantly with increasing number of charges on the network chains and chain rigidity.

The simplest theory of the collapse transition of single polyelectrolyte chains in dilute solutions is reconsidered. A novel feature of the new treatment is that the counterions can either remain within the coil or float in the outer solution. It is shown that the latter possibility is realized in many cases; thus, for these situations, the electrostatic repulsion between the uncompensated charges plays an important role in the chain behavior. These uncompensated charges lead to a significant difference between the collapse behavior of single chains and macroscopic gels where electrostatic repulsion is normally negligible and the swelling is mainly due to the osmotic pressure of counterions kept inside the gel sample. In addition the intermediate case of microgel particles of different molecular masses is considered, and the role of counterion redistribution between polymer and solution is investigated.

The paper contains experimental results for the velocity of longitudinal acoustic wave, density, longitudinal elasticity modulus and viscosity coefficient of nanocomposite Fe-gel material with different percent content of iron nanoparticles. The concise description of the preparation technology of the samples under study is also included. The determination of the velocity and attenuation of the acoustic wave was based on the measurement of the change in the phase-frequency and insertion loss - frequency characteristics due to placing the samples between radiating and receiving transducers. The effect of magnetic field on the velocity of longitudinal acoustic wave has been also experimentally studied for the used samples. The method of the investigation was based on the measurement of the change in phase of output signal due to variation of magnetic field. It has been stated that the longitudinal modulus of elasticity increases with growing frequency of excited bulk acoustic wave and the velocity of longitudinal acoustic wave shows an enhancement up to 1.75 percent with the increase of magnetic field intensity to 10 kOe.